Production or treatment of artificial filaments, threads, foils, and the like



Patented May 3, 1938 UNITED STATES PATENT OFFIE PRODUCTION OR TREATIWENT OF ARTIFI- CIAL FILAMENTS, THREADS, FOILS, AND

THE LIKE No Drawing. Application May 2'7, 1933, Serial No. 673,308. In Great Britain June 16, 1932 16 Claims.

This invention relates to the manufacture of artificial filaments, threads, ribbons, foils and the like and particularly to artificial filaments,

threads, ribbons, foils and the like having a reduced, subdued or modified lustre.

We have discovered that by incorporating certain carbohydrate materials in artificial filae ments, threads, yarns, ribbons, foils and thelike, products having a very satisfactory subdued or modified lustre may be obtained. The substances Which are used according to the present invention are organic derivatives of mono-, diand polysaccharides, such as starches, sugars and similar compounds, for example cereal starches, soluble starch, glycogen, lichenine, inulin, dextrin, sucrose, dextrose and glucose, and particularly esters of such compounds, for example the acetates, laurates, palmitates, stearates, benzoates and other aliphatic or aromatic acid esters.

According to the present invention, therefore, artificial filaments, threads, yarns, ribbons, foils and similar products having a reduced, subdued or modified lustre are obtained by introducing therein finely divided organic derivatives of the mono-, dior poly-saccharoses such as starches, sugars, dextrin, glycogen, lichenine, inulin and similar carbohydrate materials, and particularly esters of such compounds, for example the.ace tates, laurates, palmitates, stearates and benzoates. Feculose is an example of a poly-saccharose derivative which has been found very suitable for the purpose of the present invention. The saccharose derivatives are incorporated in [the artificial materials in a finely divided form,

either by introducing them into the spinning solution or other composition from which the,

artificial materials are obtained or by treating the materials after their formation with suitable ,imedia containing the finely divided derivatives. In either case, however, the saccharose'derivatives will be incorporated in an undissolved state and not in solution. Thus, when they are incorporated in the spinning solutions or other tcompositions from which the artificial materials are formed, they will be chosen so that they are insoluble in the solvent present in such compositions. For this reason esterification products of low ester content which are insoluble in acetone or other organic solvents, are particularly valuable in the case of the production of artificial materials having abasis of organic derivatives of cellulose. I

The compounds used are incompatible with the base of the artificial materials. Further, they are preferably dissolved or easily swollen by treatment with hot water or hot aqueous media e. g. soapsolutions.

The invention is of value in connection with the production of artificial materials having a reduced, subdued or modified lustre from cellulose derivatives generally, both of the regenerated cellulose type, such as are obtained by the viscose, cuprammonium and nitrocellulose processes, and also those containing organic derivatives of cellulose, e. g. cellulose fcrmate, acetate, propionate, butyrate, nitroacetate and other esters or mixed esters of cellulose, ethyl, butyl and benzyl cellulose and other cellulose ethers or mixed ethers and mixed cellulose ether-esters, for example ethyl cellulose acetate and oxyethyl cellulose acetate. It is however of particular value in connection with cellulose acetate and it will therefore be described in the specification with particular reference thereto.

Ilhe finely divided substances may be incorporated in the materialsafter their formation, for example by treating the materials with a dispersion of the delustring compound, advantageously in the presence of a swelling agent for such materials, but preferably the delustring substance is incorporated in the spinning solutions from which the artificial products are obtained. Such solutions may be spun by dry or wet spinning processes, but when wet spinning processes are em ployed, it is of course desirable that the coagulating bath should not exert any pronounced solvent action upon .the starch ester or other delustring compound used.

The incorporation of the delustring compound in the spinning solution may be carried out in any suitable manner, for example by working it with the cellulose derivative or the solvent or part of the spinning solution itself, or, if desired, it may be worked up with any other suitable medium, preferably one which is miscible with the solvent of the spinning solution, and then incorporated in the spinning solution itself or a constituent thereof in the form of a dispersion in the medium employed for working up.- Thus, the delustring substance may be worked up with acetone and a small quantity of cellulose acetate or other constituents of the spinning solution. It is necessary, in order that the particles of the substance should pass the filters and spinning nozzles without causing obstruction, that the delustring agents should be ground to a fine state of subdivision. The addition of a solution of the delustring compound to a spinning solution in which it is insoluble, affords a means of obtaining the delustring compound in a finely divided form. Whilst particle sizes up to .006 mm. diameter are permissible it is preferable that the average particle size be not more than .003 mm. diameter and particles having sizes between .001 and .002 mm. diameter have been found of especial value. In order to attain this high state of subdivision the delustring compound must usually be submitted to a grinding operation. Such a grinding operation may be carried out in a ball, tube or other suitable mill, the grinding being carried out either on the dry material or in the presence of liquids. Thus, for example feculose may be mixed with acetone to form a 10-30% dispersion and ground until a suitable particle size has been obtained, e. g. from 1 to 2 microns and the dispersion may then be incorporated in the main bulk of the spinning solution. Again, the substance may be ground in the presence of the spinning solution itself or a portion thereof, for example in the presence of an acetone solution of cellulose acetate. The finely divided substances, if not already incorporated in the solvent for the spinning solution or in the spinning solution itself, may be worked therein in any desired manner. In order to improve the state of dispersion the grinding operation may be carried out on the delustring compound in the presence of the solvent or the spinning solution or part only thereof together with dispersators and/or protective colloids for example Turkey red oil (preferably present in relatively small proportions) and/or oils such as oleic acid, linseed oil, olive oil or the like. The resulting aqueous or oily pastes of the substance may if necessary be worked with the solvent or with the main bulk of the spinning solution.

Any suitable proportions of the delustring material may be incorporated in the artificial products, for example, from 1 to 5% or 10% or even more, but in practice proportions of the order rivatives which have a very satisfactory, subof from 2 to 5% have been found particularly suitable.

As statedv above, products. may be obtained by the incorporation therein of carbohydrate dedued lustre. t has however been found, and this also forms an important part of the present invention, that a still greater delustring effect may be obtained in a very simple manner by treating the materials containing the carbohydrate derivatives with a simple scouring process, which may be carried out, for example, with an ordinary soap solution at temperatures of from to 85 C. for periods of l to 2 hours, or by similar treatments, as, for example, by dyeing with S. R. A. colours from typical soap baths at -85 C., when dyeing and delustring take place simultaneously. Water or other aqueous liquids may likewise be 'used for such after-treatments. In this manner a relatively high degree of delustre may be obtained.

The process has the additional advantage that even in materials dyed black or in other dark shades, for example dark blue, the feculose and other delustring compounds are capable of producing an appreciable reduction in lustre, which is remarkable when it is considered that delustred materials in general are relustred on dyeing in black or other dark shades.

The scouring or similar treatment may of course be carried out at any stage, for example on hanks or skeins, on mixed yarns which contain in addition to the artificial filaments natural vegetable or animal fibres, or on fabrics or manufactured articles such as stockings whether wholly or only partially made from the products of the present invention. Further, the treatment may be applied to dyed or undyed products, or simultaneously with dyeing.

Not only, as has been shown above, have the materials treated according to the present invention a very satisfactory degree of delustre, particularly after scouring, but also they retain to a great extent the tenacity and extensibility of the untreated yarn.

When the delustring agents of the present invention are incorporated into materials containing cellulose acetate or other cellulose derivatives having a relatively low melting point the agent may be chosen so that it causes scorching of the material at a temperature below that at which the cellulose derivative begins to melt. Precesses for the production of cellulose derivative materials containing such substances are described in British Patent No. 352,058 and the present invention therefore includes the simultaneous delustring and reduction of the temperature of scorching of cellulose derivative materials.

The process of the present invention may be carried out in conjunction with other delustring processes. Thus in addition to the feculose or other material employed according to this invention, other delustring agents, e. g. titanium dioxide, barium sulphate, calcium sulphate and china clay may be employed. In order to improve the opacity obtained by the use of the delustring agents of the present invention there may, if necessary, be incorporated with the said delustring agents a small proportion of a black or other dark coloured substance which may be either organic or inorganic in nature. Such black or dark coloured substance may be added for example in a proportion of 1 to 2% of the delustring agent, but should not in any case be present in so great an amount as to produce a darkening of the colour of the filaments or other materials produced.

The products obtained by the process of the present invention may be netted, woven or knitted, or associated with normal filaments or threads of cellulose acetate or other artificial silks, or with fibres of other materials such as cotton, wool, natural silk and the like to obtain special effects, and the invention also comprises the use of the delustred materials for such purposes and the products obtained thereby.

Further, fabrics and similar materials may be treated to incorporate therein the: delustring compounds of the present invention, and if desired, may subsequently be subjected to a scouring or similar treatment, or, preferably, the scouring or similar treatment may be applied to fabrics and the like made from products spun from solutions containing the delustring compounds.

The following example serves to illustrate the invention but is not to be considered as limiting it in any way.

Example spun by any suitable method. The yarn produced may be woven into fabric and dyed any desired shade from a soap bath at 75 to 80 C. employing known methods with dispersed waterinsoluble dyestufis. A dyed material of pleasantly subdued lustre may be thus obtained. It is to be understood that by the term saccharose used in the foregoing description and in the following claims is meant a substance of the nature of starch, sugar and similar substances, and the term is not to be read as including cellulose.

What we claim and desire to secure by Letters Patent is:-

1. In a process for the. manufacture of artificial filaments, yarns, ribbons, foils and like materials of subdued lustre by extruding a solution into a setting medium, the step of adding to the solution containing a substance selected from the group consisting of cellulose and its derivatives as base for the artificial materials, fine particles of an organic derivative of a saccharose insoluble in the said solutionand in the said base.

2. In a process for the manufacture of artificial filaments, yarns, ribbons, foils and like materials of subdued lustre by extruding a solution into a setting medium, the step of adding to the solution containing an organic derivative of cellulose fine particles of an organic derivative of a saccharose which is insoluble in the said solution and in the said organic derivative of cellulose.

3. In a process for the manufacture of artificial filaments, yarns, ribbons and like materials of subdued lustre by extruding a solution into an evaporative atmosphere, the step of adding to the solution containing cellulose acetate fine particles of a carboxylic acid ester of a saccharose which is insoluble in the. solution and in said cellulose acetate.

4. In a process for the manufacture of artificial filaments, yarns, ribbons and like materials of subdued lustre by extruding a solution into an evaporative atmosphere, the step of adding to the solution containing cellulose acetate fine particles of feculose.

5. In a process for the manufacture of artificial filaments, yarns, ribbons and like materials of subdued'lustre by extruding a solution into an evaporative atmosphere, the step of adding to the. solution containing an organic derivative of cellulose fine particles of a carboxylic acid ester of a starch, which ester is insoluble in the spinning solution and in the organic derivative of cellulose, has an average particle size between .0 01 and .002 mm, and is present in proportions of 2 to 5% calculated on the weight of the organic derivative of cellulose present.

6. Process for the manufacture of artificial filaments, yarns, ribbons and the like of subdued lustre, which comprises forming a solution containing an organic derivative of cellulose and fine particles of an organic derivative of a saccharose, which saccharose derivative is insoluble in the solution and in said organic derivative of cellulose, extruding said solution through a shaping device into an evaporative atmosphere and subjecting the formed materials to a scouring operation.

7. Process for the manufacture of artificial filaments, yarns, ribbons and the like of subdued lustre, which comprises forming a solution containing cellulose acetate and fine particles of a carboxylic acid ester of a starch, which ester is insoluble in the solution and in said cellulose acetate, extruding said solution through a shaping device into an evaporative atmosphere and subjecting the formed materials to a scouring operation simultaneously with the dyeing thereof.

8. A spinning solution for use in the manufacture of artificial filaments, threads, yarns, ribbons, foils and the like of subdued lustre, which comprises a substance selected from the group consisting of cellulose and its derivatives as base for the artificial materials and fine particles of an organic derivative of a saccharose, which derivative is insoluble in the solution and incompatible with the said base.

9. A spinning solution for use in the manufacture of artificial filaments, threads, yarns, ribbons, foils and the like of subdued lustre, which comprises an organic derivative of cellulose and fine particles of an organic derivative of a saccharose incompatible with the organic derivative of cellulose, which saccharose derivative is insoluble in the solution.

10. A spinning solution for use in the manufacture of artificial filaments, threads, yarns, ribbons and the like of subdued lustre, which comprises cellulose acetate and fine particles of a carboxylic acid ester of starch which is insoluble in the solution and incompatible with the cellulose acetate.

11. A spinning solution for use in the manufacture of artificial filaments, threads, yarns, ribbons and the like of subdued lustre, which comprises cellulose acetate and fine particles of feculose.

12. A spinning solution for use in the manufacture of artificial filaments, threads, yarns, ribbons and the like of subdued lustre, which comprises an organic derivative of cellulose and a finely divided carboxylic acid ester of a saccharose, which ester is insoluble in the spin ning solution and in the organic derivative of cellulose and has an average particle size not exceeding .006 mm.

13. A spinning solution for use in the manufacture of artificial filaments, threads, yarns, ribbons and the like of subdued lustre, which comprises an organic derivative of cellulose, fine particles of a carboxylic acid ester of a starch, which ester is insoluble in the solution and incompatible with the cellulose acetate, and fine particles of an insoluble opaque inorganic substance.

14. Artificial filaments, threads, yarns, ribbons and the like of subdued lustre, comprising an organic derivative of cellulose and having distributed therein fine particles of a carboxylic acid ester of a starch incompatible with the said organic derivative of cellulose.

15. Artificial filaments, threads, yarns, ribbons and the like of subdued lustre, comprising cellulose acetate and having distributed therein fine particles of feculose.

16. Artificial filaments, threads, yarns, ribbons and the like of subdued lustre, comprising cellulose acetate and having distributed therein a finely divided carboxylic acid ester of a starch, which ester is incompatible with the cellulose acetate, has an average particle size of .0'01-.002 mm. and is present in proportions of 2-5% based on the weight of the cellulose acetate.

CAMILLE DREYFUS. GEORGE HOLLAND ELLIS. 

